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Access Type

WSU Access

Date of Award

January 2011

Degree Type


Degree Name




First Advisor

Jeremy J. Kodanko


An unnatural amino acid HPN, possessing a 2-pyridylmethylene group, which is a common fragment of several multidendante polypyridyl ligands, has been designed and synthesized.

We have demonstrated a divergent strategy for attaching polypyridyl ligands into peptides. Pyridyl- containing amino acids were introduced into peptide chains. Transformation of the silyloxy functionality into a chloride leaving group, followed by N-alkylation with a secondary amine such as bis(2-dipicolyl)amine was used to attach various ligands to the peptide in a divergent fashion. In addition, changing the position of the unnatural amino acid within the peptide chain could facilitate the insertion of ligands at various positions.

Finally, we showed the generation of bis-fÝ-oxo-bridged dinuclear metallic centers based on TPA on a synthetic peptide. In addition, we demonstrated that putting two ligands on a peptide backbone increased the stability of these species compared to parent TPA complex 21' under the identical reaction conditions. Different linkers on the peptide chain and distance between the metal-binding units also play a crucial importance on the stability of this species. Time vs. absorbance plots noticeably signified that changing the ligand concentrations, formation and decay rates of the complexes 21', 63a', 63b', 63c' and 63d' can be modified. Dimetallic complexes were characterized by UV-vis spectroscopy, EPR spectroscopy and high resolution mass spectrometry.

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